Process of treating oily materials.



CABLE-TON ELLIS, 0F MONTGLAIR, NEW JERSEY. I

I BOCESS OF TREATING OILY MATERIALS.

No Drawing.

To all whom may concern.

Be it. known that I, CARLn'ron Ems, a citizen of the United States, anda resident of Montclair, in the county of, Essex and State of NewJersey, have invented certain new and useful Improvements in Processesof Treating Oily Materials, of which the following is a specification.This invention relates to the catalytic hydrogenation of oil and relatesparticularly to the hydrogenation or hardening of fatty. oils normallyso constituted as to largely inhibit the effective action of thecatalyzer'i'n the hydrogenation operation, and further relates to thehydrogenation of marine animal oils, including fish, whale and cod oiland to the products of such treatment. i I 7 Many oils contain traces ofsulfur, phosphorus, arsenic, cyanid derivatives, chlorin, iodin andother bodies more or less toxic to certain types of catalyzers, whichtoxic vbodies are oftentimes present in oils and fats in such mlnutetraces as to be scarcelydetectedby analysis, yet being present in anamount sufiicient to inhibit or utterly destroy the activity ofcatalytic bodies. Ordinary refining processes do not usually removethese toxic bodies in a satisfactory manner, although in some cases afairly complete removal is secured, but oftentimes the refining processconducted as it usually is to remove coloring matter and albumins, notonly does not throw down all the cata= lyzer toxins, but sometimes evenintroduces traces of chlorin or other undesirable bodies.

The traces of catalyzer poisons cause much trouble and loss inhydrogenation, not only by reducing the life of the catalyzer but bymaking its activity so uncertain that the output, of a plant may varyfrom day to day and cause much perplexity and annoyance because of theuncertainty of the operation.

My invention has to do with the elimination of these bodies or partialor complete reduction of their action and in the preferred form itinvolves the treatment of the oil or fat with a metallic body ormetalliferous compound capable of reacting with or absorbing a part orwhole of the-poison so that by filtration the oil may be more or essfreed from traces of toxic bodies.

Specification of Letters Patent.

Application filed March 15, 1915. Serial No. 14,524.

.- treatment.

Patented Nov. so, act a.

In carrying out this step I may add to the material to be detoxicated ametal such as alummum, nickel, iron,'copper, zinc. and the like or theiroxids or suboxids or their hydrates or other metalliferous materialreferably in a finely divided or colloidal orm, preferably heating theoil and stirring or grinding same with the detoxicator, as the toxinremover or eliminator may be termed, until the desired combination orocclusion of the poison has occurred. The oil may then be filtered toremove the detoxicator and accumulated poison, catalyzer added to theoil and hydrogen or hydrogen-containing gas passed into the oil untilthe latter has been hardened to the desired consistency. Thetemperature, pressure of the gas and the like are to be regulated withreference to the nature of the oil treated and the catalyzer employed inthe manner well known in the art.

From say one to five per cent. or so of the detoxicator maybe used, theproportion to be regulated by the character of the oil.

When the latter is strongly acid through the presence of fatty acids,soaps may form which dissolve in the oil and these may be decomposed byboiling with aqueous mineral acids such as hydrochloric acid.

The temperature may be regulated under ordinary conditions of operationas the detoxicating action or reaction usually is facilitated by theapplication of heat, temperatures between 100 and 250 C. bein the mostdesirable range, and 170190 usually being the desirable limits withheavy metal detoxicators, especially when neutral oil is being treated.When the oil is rather highly agild lower temperatures are often prefera e. The metal detoxicator should, as stated, be in a finely dividedcondition as it is important to secure a very large surface for exposureto'so viscous a liquid as an oil, especially when it is necessary toremove such minute traces. A fine or extended condition of the metal orother detoxicator is, moreover, important and it isalso desirable tobring the finely divided material into thorough contact with the oilasby stirring forcibly, or by grinding 01; 9 1161 Similar Oxids,hydrates, carbonates and the like ma be reduced by heating in thepresence of ydrogen, water gas, hydrocarbon vapors and the like and thusthe metal is obtained in a very finely divided condition. Fullers earthand pumice ground to fine dust may be treated, or in the case of thelatter, impregnated with a solution of the metal and the reduction thencaused to take place, thus spreading and extending the detoxicator to adesirable degree.

The 'mixture of the metal and its oxids or other compounds may be used,or of one metal with the oxid of another metal or two metals may bemixed as, for example, copper and aluminum. The catalyzer which isspent, that is to say, has lost its efficiency as a catalytic agent inoil hardening processes, may be used as a toxin absorbing or 'occludlnga ent as it is yet effective for such purposes a er its catalyticproperties are lost. This is especially true of a catalyzer which hasbeen injured by oxidation rather than by toxic action, such oxidationperhaps occurrlng through the presence of oxygen in the hydrogen gasused for the oil hardening operation.

In the case of oils which are heavily charged with alubumin andmucins,-treatment with one-half of one-per cent. of for- V maldehyde gasor solution is desirable before detoxication in accordance with the avery fine state of division in order to ac complish highly satisfactoryresults with a bod of the viscosity of oils and fats.

ere the terms oil and fat are used throughout this specification theyare synonymous and the terms detoxicator and detoxicatlon referrespectively to materials capable of removing small or minute quantitiesof toxic materials and to the process of such removal. 7

According to the present process the treatment of the oil may if desiredprogress in two stages. In the first sta e thereof the o1l is entirelyor substantial y freed from lnhibltors of catal sis and in the second ethe oil is sub ected to treatment with stag hy rogen in the presence ofa catalyzer.

The treatment of the oil in the first stage should be carried out withrespect to the' which cannot be readily removed by distillaticn the oilmay be subjected to treatment with alkali to form a soap with the fattyacids and acid resins, which soap being of a colloidal character absorbsfrom the oils various undesirable bodies which have an inhibiting actionon catalyzers. The soap is removed by settling and the resulting more orless nearly neutral oil is treated with a finely divided detoxicator andis subjected to the second stage which may be carried out illustrativelyas follows: A quantity of nickel hydrate or carbonate is heated with asmall quantity of the oil to about 260 C, while hydrogen or otherreducing gas is passed through and when the nickel material hasbeensufiicientlyreducedit is added to about twenty times its weight of theoil from the first stage of the operation;

The temperature is maintained at 180 to 200 (3., and hydrogen is passedthrough the oil while the catalyzer is maintained in a state ofagitation by the passage of the gas through the oil, or if desired bymechanical stirring. The temperature may be reduced below this ifdesired, as for example between 150 to 170 C. By proceeding in thismanner after a short space of time the oil is hardened to a consistentfat as hard as or harder than tallow or stearin.

As a more specific illustration of the method, a grade of cod oil havingan acid number of about 25 and a percentage content reckoned as oleicacid of one-half this number or 12%, was treated with an amount ofcaustic soda or ammonia in aqueous solution, sufficient to unite withthe fatty acids.

The alkali and oil were agitated at to 75 C. for a short time and thesoap al lowed to settle. The oil was then washed with water and agitatedfor one hour at 180 C. with 5% of freshly precipitated cop per hydrate.The latter was then allowed to settle and was filtered off; A smallamount of copper remained in solution in the oil, or in a colloidalcondition. A suitable quantity of the nickel material as above indicatedwas added, and the oil was then treated with hydrogen. In a few hoursthe oil readily hardened to a fat melting at 53 C. The small amount ofcopper remaining in. the oil during the hydrogenation step was largelyremoved with the cata lyzer, on final filtration.

Another sample of this same oil, treated without the detoxicating stepfor several.

days with hydrogen in the presence of a nickel catalyst, showed novisible hardening. In the manufacture ofoils intended for edible urposesit is customary to wash out free acid with alkali as a small amount offree acid gives the product an undesirable rancid flavor or the changeswhich develop acidity are enerally accompanied by that change in avorreco ized as rancidity. Crude oils intended or edible purposes shouldhave a relatively small content of free fatty acid. For example in thecase of cottonseed oil the crude oil. which Is to be used for ediblepurposes-should contain only a few percent. of free fatty acid. Iflarger amounts are present the oil is generally regarded as undesirablefor preparing edible products and the oil is .used for soap making orother industrial purposes, I

where the presence oflarger amounts of free fatty acid is of lessimportance. In the case of soap fat the presence of fatty acid is of nodisadvantage and in fact is an aid in saponification. Therefore, withlow grade oils such as the marine animal oils mentioned which supposedlywere not ada ted for edible purposes, in making use oft ese in theinedible field no attention for the purposes hereof has been paid to thepresence of free fatty acid. In making soap, as stated, the presence offree fatty acid is not objectionable. Attempts to .harden these oils forindustrial purposes have been directed toward the treatment of the crudeor slightly clarified oil,-without successful results as indicated. Theteachings from various publications have led workers in thehydrogenation field to assume that oleic acid was as readilyhydrogenated as a neutral glycerid. In consequence the removal of freefatty acid and other inhibitors of hydrogenation by the procedure hereillustratively set forth above has not been practised to my knowledge.

When it is desired to remove glycerin from a highly acidoil, at the sametime converting the unsaturated into saturated bodies, the fatty acidmay be removed as indicated, the oil hydrogenated, and the productsaponified by the autoclave process or otherwise and the glycerid thusobtained. The removal of the fatty acid also enables hydrogenation to becarried out with catalyzers of the nickel oxid type withoutobjectionable solution of the nickel in the oil, so that productsadapted for edible purposes may be obtained without any toxic quantitiesof nickel.

The process may be carried out with various oils of the charactermentioned and materiah Or the soda soa higher, temperatures areemployed, carbonization and blackening do not occur.

Hydrogen or a hydrogen-containing gas may be used at ordinary pressureor at higher pressures if desired.

The removal of any resinous inhibitors of catalysis may be effected bytreatment of the oil with caustic soda or potash. Or milk of lime may beemployed for this purpose to produce a lime soap which effectively,removes the last traces of the nudesirable resin-like bodies. This maybe carried out by combinin the major portion of the free fatty acid withsoda or potash and then adding a quantity of lime suflicient to combinewith the remaining fatty acid so as to more effectively occlude theresinous may be settled and removed and lime ad ed to afford the finaltreatment. Other alkaline earths such as barium hydroxid may also'beemployed.

The removal of the entire amount of fattyacid or such part of'it as isrequired may be carried out with carbonated alkali or caustic alkali.

The interrelation which exists between the stage of removal of theinhibitors of catalysis and the hydrogenation stage establishes acorrelation between the two stages which constitutes a homeogeneousprocess.

While spent nickel catalyzer may be used for detoxlcating 'oil in someinstances, in other cases nickel material which has been reduced byhydrogen or otherwise subjected to rather high temperatures does notappear to be in the right condition for absorbing catalyzer poisons tothe extent desired. Copper is particularly serviceable especially whenused in a form of freshly precipitated copper hydrate. The ordinarycommercial form of copper carbonate I have not found so effective inthis connection. Copper is especially desirable in the treatment ofinedible fats, while other detoxicating agents may be used for thepreparation of edible products although copper is likewise suitable forthis purpose provided it is substantially. or entire y eliminated fromthefinal product. 1

" In treating the oil with copper hydrate lit which may take place underthese conditions. 7

From menhaden or cod oils a substantially neutral product may beobtained which has a hardness ranging from lard or tallow to brittleproducts of high melting point. So far as I am advised it has not beenheretofore possible to prepare these desirable hard brittle products bythe hydro genation of marine animal oils. Products useful in stuffingharness leather or other leather material may be prepared from menhadenor cod oil by hydrogenatin g to a melting point of about 125 F. heitscale is used in this connection because of the practice in the leathertrade of expressing the melting point of leather stuifing on thisscale.) Animal fats 'such as stearin havin a fatty acid content of morethan 2% are liable to spewor cause a bloom on the leather and are rearded as objectiona-ble for the purpose af present process the acidityof the .oil may be reduced to below 2% or even to form a neutral oil andthe product hardened to 125 F. affording a fatty material which is ofutility in the leather trade. The removal of sulfur also is desirable.

The treatment of oils in a liquid state with finely divided detoxicatingmaterial with the ability to hydrogenate the product as a liquid fatobviates the difficulties heretofore experienced through attempting tovolatilize fatty material and pass over catalyzer for the urpose ofhardening the fatty material. fVhlle it is possible to volatilize afatty acid, glycerids cannot be so treated without marked decomposition.The resent rocess enables fats'to be handled in a liquid state toproduce useful commercial products. Thus low grade oils which haveheretofore been regarded as in- V capable of hydrogenation are now madeuseful in the arts.

The soao obtained by the neutralization of free. fatty acid may betreated with sulfuric acid to liberate the fatty acid and thesesulfonated to form sulfonated oil material suitable for textile purposesor in the leather industry. In the latter field the sulfonated cod oilor other fish oil is in de-' he Farenoresaid. By the mand andconsequently the entire fatty ma the hydrogenated cod or menhadenoil'orother similar marine animal oil, more particularly byincorporating such hardened product with an oil such as good qualitycottonseed oil. Lard substitute may be prepared by meltin 10 to 15 partsof highly hydrogenated cod oil of a neutral character and incorporatingwith'90 to 85 parts of cottonseed oil. The product is preferably chilledto cause a quick set.

The detoxicating agent enables the removal of sulfur 0r iodin or similardisturbing element which may be objectionable in edible fats. By theremoval of sul fur there is less tendency to the formation of sulfuretedor other sulfur compound. In

a similar manner by the removal of iodin the objection to the presenceof iodin in edible fats of everyday consumption is eliminated. Theproportion of hardened cod oil or other hardened fish or whale oil tocottonseed oil may be varied or other vege-' table oils such as corn oiland the like may be similarly employed. Fish oil and cottonseed oil maybe co-hydrogenated.

To recapitulate, my invention is concerned with or involves treating ina liquid condition oils and fats containing catal zer poisons, oftenpresent only as traces, w ich treatment comprises adding to the oil orfat a detoxicating material preferably a finely divided or pulverulentmaterial or metalliferous or oxid or hydroxid material (such as basiccopper material preferably copper hydrate) having an affinity for saidpoisons, but preferably substantially without other effect or action onthe oil or fat, preferably suspending the detoxicator in the oily mediumas by rapid stirring, preferably heating, usually between 100 and 200 C.andcontinuing such conditions until the poison is absorbed by thedetoxicator to the degree desired or necessary, then if desiredintroducing active catalytic material and hydrogen so as to harden theoil to the required consistency, the detoxicator preferably beingremoved before the addition of the active catalytic material. By suchprocedure a neutral hardened fat may be obtained from strongly acidmenhaden and cod or other I rial and thereupon hydrogenating the latter.

naaaeie of absorbing catalyzer poisons comprising.

cop er hydrate, in intimately contacting the fine y-divided materialwith the oil under suitable thermal conditions and in subsequentlyfreeing the fatty material from the finely-divided material; whereby thesaid fatty material is sufliciently freed from destructive'catalyzerpoisons.

3. In the process of hydrogenating fatty material and the like theimprovement which coin rises incorporating therewith, a finely divi edbasic compound of a metal, which compound is capable of combining withany sulfur-containin substances which could have a harmful-e ect upon anickel catalyst, whereby such sulfur-containing substances are convertedinto insoluble bodies, and thereafterintimately contacting the materialwith the finely-divlded body under suitable thermal conditions and insubsequentlyremoving the finely-divided body.

4. The process of treating oil which comprises the step of exposing anoil containing catalyzer poisons to the action of a basiccopper-containing compound capable of detoxicating the said oil.

5. In the process of hydrogenating oil the step which comprises exposingan oil containing bodies tending to poison nickel catalyzer'to theaction of a finely-divided copper body capable of detoxicating said oil,in subsequently substantially removin the copper material and absorbednicked poisons and in subjectin the detoxicated oil to the action of hyrogen and nickel catalyzer. a

6. The process of treating oil which comprises the step of exposing anoil containing catalyzer poisons to the action of copper hydrate, invigorously stirrin the oil to be detoxicatcd, in maintaining sultablethermal conditions during such stage and in thereupon eliminating thecopper hydrate with more or less catalyzer poisons combined or occludedtherewith; whereby the oil becomes fitted for normal catalytichydrogenation.

7. The process of hydro enating fish and whale oils having a relative yhi h acid content and which are not capab e of being readilyhydrogenated by the action of h drogen in the presence of a nickel catayzer, which comprises treating said oil with copper-containing bodiescapable of substantially removing from such oil the constitu- 1 entsinhibiting catalysis so that the resulting oil will readily hydrogenatewhen sub jected to the action of hydrogen in the presence of acatalyzer.

8. Th process of detoxicating fish and whaleoils containing sulfur andwhich are not capable of being readily hydrogenated by the action ofhydrogen in the presence of a nickel catalyzer, which comprises heatingthe oil with a basic compound of copper capable of removing the sulphur.

9. The process of detoxicating oils containing sulfur and which are notcapable of'being readily hydrogenated by the action of hydrogen in thepresence of a nickel catalyzer, which comprises'heating such oil with anamount of copper hydrate sufficient to substantially completely removethe inhibitors of catalysis so that the resulting oil will hydrogenatewhen subjected to the action of hydrogen in the presence ofnickelcatalyzer.

.10. In the processof hardening fatty material such as animal orvegetable oils with .the aid of nickel catalyzer the step whichcomprises adding to the oil in a liquid state a finely-divided basiccopper-containing substance capable specifically of removing poisonsfrom the oil which inhibit the act1on of nickel catalyzers.

11. In the catalytic hydrogenation of oils, the step prior to thetreatment with hydrogen, which comprises subjecting an oil containingchlorin and sulfur impurities capable of acting as catalyzer poisons, tothe action of a copper-containing detoxicating agent capable of removingsaid chlorin and sulfur impurities, while maintaining said oil in aliquid state;

12. The process of treating fatty material such as animal or vegetableoils which comprises addin to the oil in a liquid state finely-dividecopper hydrate capable of re moving catalyzer poisons from the oil andin subsequently subjecting the oil to the action of hydrogen in thepresence of a nickel catalyzer.

13. In the process of treating fatty material, the herein describedimprovement which comprises hydrogenating with a nickel catalyzer an oilcontainin dissolved copper and in subsequently su stantially freeing theoil from traces of nickel and copper.

14. The 'process of treating oils comprising treating fatty oil with abasic compound of a metal which compound is capable of detoxicating saidoil and thereafter hydrogenating the detoxicated oil in the presence ofa hydrogenating catalyzer.

15. In the treatment of oily materials conto form oil-insoluble bodies,and thereafter 1 removin at least the major portion of such oil insouble bodies; thereafter addin a hydrogenatingcatalyst and passing byrogen in contact with said oil.

16. A process which comprises adding to a fatty oil containingunsaturated components and materials inimical to catalytic hydrogenationof such components, a basic compound of a metal, which compound is freefrom active substances capable of exerting a poisoningefi'ect upon suchcatalytic hydrogenation, removing at least a portion of the products ofsuch treatment -from the 10 oil, and thereafter subjecting the oil tothe action of hydrogen in the presence of a catalyst capable ofefiecting hydrogenation.

Signed at Montclair, in the county of Essex and State of New Jersey,this 12th day of March, A. D. 1915.

IOAKRLETON ELLIS.

I Witnesses:

W. O. HENKE, I A. A. Wms.

